CN111387281B - Preparation method and application of fruit and vegetable sterilization and preservation complexing agent - Google Patents
Preparation method and application of fruit and vegetable sterilization and preservation complexing agent Download PDFInfo
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- 230000001954 sterilising effect Effects 0.000 title claims abstract description 46
- 238000004321 preservation Methods 0.000 title claims abstract description 39
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 31
- 239000008139 complexing agent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 235000012055 fruits and vegetables Nutrition 0.000 title claims description 48
- 229940088598 enzyme Drugs 0.000 claims abstract description 57
- 108090000790 Enzymes Proteins 0.000 claims abstract description 47
- 102000004190 Enzymes Human genes 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 30
- 239000004366 Glucose oxidase Substances 0.000 claims abstract description 30
- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 30
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 30
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920002148 Gellan gum Polymers 0.000 claims abstract description 17
- 239000000216 gellan gum Substances 0.000 claims abstract description 17
- 235000010492 gellan gum Nutrition 0.000 claims abstract description 17
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000008103 glucose Substances 0.000 claims abstract description 16
- 229920002907 Guar gum Polymers 0.000 claims abstract description 11
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- 235000010417 guar gum Nutrition 0.000 claims abstract description 11
- 229960002154 guar gum Drugs 0.000 claims abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000004471 Glycine Substances 0.000 claims abstract description 8
- 239000001110 calcium chloride Substances 0.000 claims abstract description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
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- 239000003795 chemical substances by application Substances 0.000 claims description 24
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- 239000000203 mixture Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 11
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
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- 238000004090 dissolution Methods 0.000 claims description 6
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 5
- 229960002446 octanoic acid Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 239000005643 Pelargonic acid Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 7
- 229920001282 polysaccharide Polymers 0.000 abstract description 6
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 3
- 206010016807 Fluid retention Diseases 0.000 abstract description 2
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- 230000009286 beneficial effect Effects 0.000 abstract 1
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- 235000013311 vegetables Nutrition 0.000 abstract 1
- 235000004936 Bromus mango Nutrition 0.000 description 15
- 235000014826 Mangifera indica Nutrition 0.000 description 15
- 235000009184 Spondias indica Nutrition 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 241001093152 Mangifera Species 0.000 description 13
- 241000219094 Vitaceae Species 0.000 description 11
- 235000021021 grapes Nutrition 0.000 description 11
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 10
- 235000014364 Trapa natans Nutrition 0.000 description 10
- 235000009165 saligot Nutrition 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 240000001085 Trapa natans Species 0.000 description 7
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 241000207199 Citrus Species 0.000 description 5
- 235000020971 citrus fruits Nutrition 0.000 description 5
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- 241000249058 Anthracothorax Species 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 2
- 241000228153 Penicillium citrinum Species 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009920 food preservation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WWUZIQQURGPMPG-UHFFFAOYSA-N (-)-D-erythro-Sphingosine Natural products CCCCCCCCCCCCCC=CC(O)C(N)CO WWUZIQQURGPMPG-UHFFFAOYSA-N 0.000 description 1
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010564 aerobic fermentation Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- -1 polysaccharide compound Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- WWUZIQQURGPMPG-KRWOKUGFSA-N sphingosine Chemical compound CCCCCCCCCCCCC\C=C\[C@@H](O)[C@@H](N)CO WWUZIQQURGPMPG-KRWOKUGFSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Storage Of Fruits Or Vegetables (AREA)
Abstract
The invention discloses a fruitThe invention discloses a preparation method of a vegetable sterilization and preservation complexing agent, and the preparation method adopts a coprecipitation method to prepare fatty acid modified Fe 3 O 4 The reagent takes glucose as a substrate and reacts with the glucose oxidase to generate hydrogen peroxide in fatty acid-Fe 3 O 4 Under the action of nano enzyme, active oxygen is generated by reaction, so that the antibacterial effect is achieved; the complexing agent prevents the aggregation of nano particles, increases living sites, is beneficial to capturing bacteria due to the positive charge on the surface of a composite film formed after use, can generate serial catalytic reactions due to glucose oxidase loaded on the composite film, is polysaccharide due to gellan gum and guar gum, and has good moisturizing performance; when in use, calcium chloride, glycine and glucose are used as auxiliary materials, so that the effects of improving the water retention of the membrane and regulating the osmotic pressure of cells are achieved; has the characteristics of sterilization, moisture retention and good film forming property, and can effectively prolong the shelf life of fruits.
Description
Technical Field
The invention belongs to the technical field of agricultural fruit and vegetable fresh-keeping, and particularly relates to a preparation method and application of a fruit and vegetable sterilization and fresh-keeping complexing agent.
Background
The food packaging material is an important factor influencing the storage period of food, the common packaging material is a plastic product at present, the packaging material can effectively delay the rotting speed of the food and prolong the storage period of the food, but the long-term use of the packaging material can influence the quality of the food and pollute the environment, the research on the more environment-friendly and green food preservation material is of great significance, and the green, safe and degradable food preservation material becomes a research hotspot.
The gellan gum is a carboxylated extracellular polysaccharide secreted by organism sphingosine unicellular bacteria under the aerobic fermentation condition, and has the advantages of small gelling amount, good gel forming capability, high transparency, good compounding property and the like. The guar gum is a natural polysaccharide compound taking galactomannan as a main component, has good film forming property and stability, and can be compounded with other polysaccharide gums to form a compound solution.
Nanometer enzyme, a kind of nanometer material with enzyme catalytic activity, mainly includes metal base nanometer enzyme, metal oxide base nanometer enzyme and carbon base nanometer enzyme. At present, the reported nano enzyme has an antibacterial effect, mainly depends on the activity of a pseudoperoxidase of the nano enzyme, and generates an antibacterial effect by utilizing the characteristic of generating active oxygen with hydrogen peroxide. The existence of hydrogen peroxide is necessary when active oxygen with bactericidal action is generated, and although hydrogen peroxide with low concentration is easy to volatilize and has oxidation-reduction property, the nanometer enzyme has certain limitation when being used as an antibacterial agent. If the hydrogen peroxide can be generated through reaction, the generated hydrogen peroxide is continuous and can overcome the defects caused by addition; there are many methods capable of generating hydrogen peroxide through reaction, wherein different biological enzymes react with different substrates such as glucose, uric acid, cholesterol and the like, and the method for detecting glucose is the most common method for generating hydrogen peroxide through reaction of glucose as a substrate and glucose oxidase; the characteristic is utilized in the field of fruit and vegetable preservation, almost no report is found, and the method is a new research field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a fruit and vegetable sterilization and preservation complexing agent, which achieves the sterilization purpose by utilizing the reaction of the complexing agent loaded with nano enzyme and glucose oxidase and glucose to generate active oxygen and is applied to the preservation of fruits and vegetables.
The invention adopts a coprecipitation method to prepare fatty acid modified Fe 3 O 4 The nanometer enzyme, glucose oxidase, gellan gum and guar gum complex agent takes glucose as a substrate, reacts with the glucose oxidase to generate hydrogen peroxide, and reacts with fatty acid-Fe 3 O 4 Under the action of nano enzyme, active oxygen is generated by reaction, so that the antibacterial effect is achieved. The complexing agent is firstly prevented from containing sodiumThe aggregation of the rice grains increases living sites, the positive charge on the surface of the composite membrane formed after the use is favorable for capturing bacteria, the glucose oxidase loaded on the composite membrane can generate serial catalytic reactions, and the gellan gum and the guar gum are polysaccharides and have good moisture retention performance.
When the fruit and vegetable sterilization and preservation complexing agent is used, calcium chloride, glycine and glucose are added in the formula, so that the effects of improving the water retention of the film and regulating the osmotic pressure of cells are achieved; the compound agent is used for fruit preservation, has good sterilization, moisture retention and film forming properties, and effectively prolongs the shelf life of fruits.
The preparation method of the fruit and vegetable sterilizing and fresh-keeping complexing agent comprises the following steps:
(1) Fatty acid modified Fe 3 O 4 Preparation of nanoenzyme
Dissolving 1.5-3 parts by weight of ammonium ferrous sulfate and 1-2 parts by weight of ferric trichloride in 40-60 parts by weight of deionized water, stirring and heating in a water bath under the protection of nitrogen, adding 4-6 parts by weight of acetonitrile solution containing 0.1-0.5 part by weight of fatty acid when a reaction solution is heated to 80 ℃, stirring the mixed solution for 5-10 min, adding 5-10 parts by weight of ammonia water, continuously stirring the reaction solution at 80 ℃ for 30-60 min, cooling to room temperature, precipitating the obtained suspension with methanol, collecting a product with a magnet, washing with methanol for 4-6 times to remove excessive fatty acid, and performing vacuum drying to obtain the fatty acid modified Fe 3 O 4 Nano enzyme;
(2) Preparation of loaded nano enzyme composite liquid
Mixing and heating 30-50 parts by weight of guar gum, 90-100 parts by weight of gellan gum and 2500-3000 parts by weight of distilled water to 80 ℃, stirring for dissolving, and adding 5-10 parts by weight of fatty acid modified Fe after completely dissolving 3 O 4 Continuously stirring the nano enzyme at 80 ℃ for 30-40 min to obtain nano enzyme-loaded composite liquid;
(3) Preparation of composite agent of loaded nano enzyme and glucose oxidase
Heating 20 parts by weight of the nano-enzyme-loaded composite liquid to 80 ℃ for complete dissolution, cooling to 50 ℃, adding 1 part by weight of glucose oxidase, and uniformly stirring to room temperature to obtain a composite agent loaded with the nano-enzyme and the glucose oxidase, namely the fruit and vegetable sterilization and preservation composite agent.
The fatty acid comprises one of caproic acid, heptanoic acid, caprylic acid, pelargonic acid and capric acid.
The mass volume concentration of the ammonia water is 28%.
The gellan gum is low acyl gellan gum or high acyl gellan gum.
The glucose oxidase activity is 8U/mL.
The invention also aims to provide the fruit and vegetable sterilizing and fresh-keeping complexing agent prepared by the method.
The invention applies the fruit and vegetable sterilization and preservation complexing agent to fruit sterilization and preservation, when in use, the fruit and vegetable sterilization and preservation complexing agent 5-10 parts by weight, calcium chloride 1-2 parts by weight, glycine 3-8 parts by weight and glucose 5-10 parts by weight are mixed, distilled water is added to complement 100 parts by weight, after stirring and mixing evenly, the fruit to be preserved is immersed in the mixed solution for 10-30 min, taken out, dried, packaged and stored at normal temperature or 4 ℃.
The invention has the advantages that:
1. the compounding agent loaded with the nano enzyme and the glucose oxidase prepared by the invention reacts with glucose to generate active oxygen including hydroxyl free radicals, peroxy free radicals and the like for sterilization, and the glucose oxidase oxidizes the glucose to continuously generate hydrogen peroxide under the catalysis of natural enzyme and the nano enzyme in the compounding agent, so that the fatty acid modifies Fe 3 O 4 Under the catalysis of the nano enzyme, high active oxygen is generated for sterilization, and the nano enzyme is used for keeping fruits and vegetables fresh, and has the effect of inhibiting the fruits and vegetables from rotting;
2. the composite membrane is used as a carrier of the nano enzyme and the natural enzyme, so that the aggregation of nano particles is prevented, living sites are increased, positive charges are carried on the surface of the composite membrane formed after the composite membrane is used, bacteria can be captured, glucose oxidase loaded on the composite membrane can generate serial catalytic reactions, and gellan gum and guar gum are polysaccharides and have good moisture retention performance;
3. the fruit and vegetable sterilization and preservation complexing agent prepared by the invention is used for fruit preservation, has good sterilization, moisture preservation and film forming properties, and effectively prolongs the shelf life of fruits.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1: composite agent loaded with nano enzyme and glucose oxidase for citrus preservation
1. Fatty acid modified Fe 3 O 4 Preparation of nanoenzymes
Dissolving 102g of ammonium ferrous sulfate and 70g of ferric trichloride in 2500g of deionized water, stirring and heating under the protection of nitrogen, and adding 175g of acetonitrile solution containing 21g of caproic acid when the reaction solution is heated to 80 ℃; violently stirring the mixed solution for 5min, adding 340g of ammonia water (w/v, 28%), continuously stirring the reaction solution for 30min at 80 ℃, cooling to room temperature, precipitating the obtained suspension by using methanol, collecting the product by using a magnet, washing the product for 4 times by using methanol to remove excessive caproic acid, and drying the product in vacuum at 60 ℃ for 12h to obtain caproic acid modified Fe 3 O 4 Nano-enzyme;
2. preparation of loaded nano-enzyme composite liquid
Mixing 2kg of guar gum, 6kg of low acyl gellan gum and 160kg of distilled water, heating to 80 ℃, stirring for dissolving, and adding 350g of hexanoic acid modified Fe after complete dissolution 3 O 4 Stirring at 80 deg.C for 30min to obtain nanometer enzyme-loaded composite liquid;
3. preparation of composite agent for loading nano enzyme and glucose oxidase
Heating 1kg of the nano-enzyme-loaded composite liquid to 80 ℃ for complete dissolution, cooling to 50 ℃, adding 50g of glucose oxidase with the activity of 8U/mL, and uniformly stirring to room temperature to obtain a nano-enzyme-loaded and glucose oxidase compound, namely a fruit and vegetable sterilization and preservation compound;
4. mixing 5 parts by weight of fruit and vegetable sterilization and preservation complexing agent, 1 part by weight of calcium chloride, 5 parts by weight of glycine and 5 parts by weight of glucose, adding distilled water to complement 100 parts by weight, and stirring and uniformly mixing;
5. orange preservation experiment: selecting fresh, uniform-sized, consistent-maturity, non-injury and pest-free citrus 10kg, soaking the citrus in the mixed solution prepared in the step 4 for 10min, and repeating for 10min once; meanwhile, distilled water is used as a blank, and the blank is naturally aired and then placed at room temperature for storage and preservation experiments;
6. comparison of bacteriostatic Properties
In the experiment, the inhibition effects of the mixture obtained in the step 4 and distilled water on penicillium citrinum and aspergillus niger are compared in a thermostat at 29 ℃ by adopting an inhibition zone method, and the inhibition performance evaluation result is shown in table 1.
TABLE 1 antibacterial property of the mixture for fruit and vegetable sterilization and fresh-keeping
As can be seen from the size of the diameter D of the inhibition zone in the table 1, the fruit and vegetable fresh-keeping mixed liquid has good inhibition effect on penicillium citrinum and aspergillus niger;
7. fresh-keeping effect of oranges
As can be seen from Table 2, the blank group begins to rot from the storage time of day 15, the oranges preserved by the mixture in step 4 begin to rot from the storage time of day 50, and the rot rate of the oranges treated by the fruit and vegetable preservative mixture is 7.1% and is obviously lower than that of the oranges not treated (43.0%) by the storage time of day 70; the reason is that the complex agent loaded with the nano enzyme and the glucose oxidase has good inhibition effect on pathogenic microorganisms.
TABLE 2 influence of the mixture for sterilizing and refreshing fruits and vegetables on the decay Rate (%) of oranges
8. Change in weight loss ratio during storage
As can be seen from Table 3, the citrus weight loss rate gradually increased with the increase of storage time, and by the end of storage (70 days), the weight loss rate of the mixture treatment of step 4 was 7.6%, which was significantly lower than that of the untreated (17.5%); the reason is that after the oranges are treated, the complexing agent forms a layer of protective film on the surfaces of the fruits, so that oxygen permeability and water permeability are reduced, transpiration and respiration of the fruits are inhibited, moisture is not easy to dissipate, and the consumption of organic matters per se is relatively reduced;
TABLE 3 influence of the mixture for sterilizing and refreshing fruits and vegetables on the weight loss ratio (%) of citrus
Example 2: composite agent loaded with nano enzyme and glucose oxidase and used for mango preservation
1. Fatty acid modified Fe 3 O 4 Preparing nano enzyme: dissolving 110 g ammonium ferrous sulfate and 55 g ferric trichloride in 3000g of deionized water, stirring and heating under the protection of nitrogen, and adding 200g of acetonitrile solution containing 20g of heptanoic acid when the reaction solution is heated to 80 ℃; after the mixed solution is vigorously stirred for 8min, 380mL of ammonia water (w/v, 28%) is added, and the reaction solution is continuously stirred for 40min at 80 ℃ and then cooled to room temperature; precipitating the obtained suspension with methanol, collecting the product with magnet, washing with methanol for 5 times to remove excessive heptanoic acid, and vacuum drying at 60 deg.C for 18 hr to obtain heptanoic acid modified Fe 3 O 4 ；
2. Preparing a loaded nano enzyme composite liquid: heating guar gum 3.3kg, high acyl gellan gum 10kg and distilled water 330kg to 80 deg.C, stirring for dissolving, adding 400g of enanthic acid modified Fe after completely dissolving 3 O 4 Stirring at 80 deg.C for 35min to obtain composite liquid loaded with nanometer enzyme;
3. heating 1kg of the nano enzyme-loaded composite liquid to 80 ℃ for complete dissolution, cooling to 50 ℃, adding 50g of glucose oxidase with the activity of 8U/mL, and uniformly stirring to room temperature to obtain a nano enzyme-loaded glucose oxidase composite agent, namely a fruit and vegetable sterilization and preservation composite agent;
4. mixing 8 parts by weight of fruit and vegetable sterilization and preservation complexing agent, 2 parts by weight of calcium chloride, 3 parts by weight of glycine and 8 parts by weight of glucose, adding distilled water to complement 100 parts by weight, and stirring and uniformly mixing;
5. mango preservation experiment: selecting 10kg of fresh mango with uniform size, consistent maturity, no damage and no pests, and soaking the mango in the mixed liquid prepared in the step 4 for 20min; meanwhile, distilled water is used as a blank, and the blank is naturally aired and then placed at room temperature for storage and preservation experiments;
TABLE 4 sensory evaluation table of 15-day storage of mangos
6. Fresh-keeping rate of mango
As can be seen from Table 5, the good mango yield after the mixture treatment in step 4 is significantly higher than that of the blank group; after the mixture is treated in the step 4, the good fruit rate of the mangoes is still 100% after the mangoes are stored for 28 days, rotten fruits appear when the mangoes are stored for 14 days in a blank group, and the good fruit rate is further reduced to 0 when the mangoes are stored for 35 days;
TABLE 5 influence of the mixture for sterilizing and refreshing fruits and vegetables on the good fruit yield (%) of mango
7. Change in weight loss ratio during storage
Table 6 shows that the weight loss rate of the mangos is 5.4% and the blank group is 8.0% after the fruit and vegetable sterilizing and fresh-keeping mixed liquid treatment in the storage process; this also shows that the treatment has a better effect on mango preservation;
TABLE 6 influence of the mixture liquid for sterilizing and refreshing fruits and vegetables on the weight loss rate (%) of mango
Example 3: nano enzyme and glucose oxidase loaded complexing agent for fresh preservation of water chestnuts
1. Fatty acid modified Fe 3 O 4 Preparing nano enzyme: dissolving 120g of ammonium ferrous sulfate and 80g of ferric trichloride in 3500g of deionized water, stirring and heating under the protection of nitrogen, and adding 250g of acetonitrile solution containing 25g of octanoic acid when the reaction solution is heated to 80 ℃; mixed liquid dramaAfter vigorously stirring for 10min, adding 400g of ammonia water (w/v, 28%), continuing stirring the reaction solution at 80 ℃ for 50min, and cooling to room temperature; precipitating the suspension with methanol, collecting the product with a magnet, washing with methanol for 6 times to remove excessive octanoic acid, vacuum drying at 60 deg.C for 20 h to obtain octanoic acid-modified Fe 3 O 4 ；
2. Preparing a loaded nano enzyme composite liquid: heating 3kg of guar gum, 9 kg high acyl gellan gum and 180kg of distilled water to 80 ℃, stirring for dissolving, and adding 600g of caprylic acid modified Fe after completely dissolving 3 O 4 Stirring at 80 deg.C for 30min to obtain composite liquid loaded with nanoenzyme;
3. the preparation method of the complex agent for loading the nano enzyme and the glucose oxidase is the same as that of the example 1;
4. mixing 10 parts by weight of fruit and vegetable sterilization and preservation complexing agent, 1.5 parts by weight of calcium chloride, 5 parts by weight of glycine and 10 parts by weight of glucose, adding distilled water to complement 100 parts by weight, and stirring and uniformly mixing;
5. water chestnut preservation experiment: washing the water chestnuts with distilled water, soaking the water chestnuts in the mixed liquid prepared in the step (4) for 10min, and repeating the steps once; meanwhile, distilled water is used as a blank, the blank is naturally dried and then placed at 4 ℃ for storage and preservation experiments, and relevant results are shown in tables 7, 8 and 9;
TABLE 7 influence of the mixture of fruits and vegetables with bactericidal and freshness-keeping effects on the weight loss ratio (%) of water chestnuts
TABLE 8 influence of the mixture of fruits and vegetables for sterilization and preservation on soluble solids (%) of water chestnut
TABLE 9 influence of the mixture of fruits and vegetables with bactericidal and freshness-keeping effects on the respiratory intensity (mg/(kg. H)) of water chestnuts
Results show that the water loss rate and the nutrient substance consumption of the water chestnuts are effectively reduced by the treatment of the fruit and vegetable sterilizing and refreshing mixed liquid in the step 4; obviously slows down the respiration process, so that the water chestnuts are always in lower respiration intensity; the hardness and brittleness of the pulp are effectively kept, and the full and firm appearance of the fruit grains is maintained; the descending trend of the soluble solid content of the water chestnut is obviously controlled.
Example 4: composite agent loaded with nano enzyme and glucose oxidase for grape preservation
1. Fatty acid modified Fe 3 O 4 Preparing nano enzyme: dissolving 150g of ferrous ammonium sulfate and 95g of ferric trichloride in 4000g of deionized water, stirring and heating under the protection of nitrogen, adding 300g of acetonitrile solution containing 33g of nonanoic acid when the reaction solution is heated to 80 ℃, violently stirring the mixed solution for 10min, adding 450g of ammonia water (w/v, 28%), continuously stirring the reaction solution at 80 ℃ for 60min, cooling to room temperature, precipitating the obtained suspension by methanol, collecting the product by using a magnet, washing the product for 6 times by using methanol to remove excessive nonanoic acid, and drying the product in vacuum at 60 ℃ for 24 h to prepare the nonanoic acid modified Fe 3 O 4 ；
2. Preparing a loaded nano enzyme composite liquid: heating 2.5 kg guar gum, 8 kg low acyl gellan gum and 250kg distilled water to 80 deg.C, stirring for dissolving, adding 300g pelargonic acid modified Fe after completely dissolving 3 O 4 Stirring for 30min at the temperature of 80 ℃ to obtain a nano enzyme loaded composite liquid;
3. preparing a complex agent of loaded nano enzyme and glucose oxidase: the same as example 1;
4. mixing 8 parts by weight of fruit and vegetable sterilization and preservation complexing agent, 2 parts by weight of calcium chloride, 3 parts by weight of glycine and 8 parts by weight of glucose, adding distilled water to complement 100 parts by weight, and stirring and uniformly mixing;
5. grape preservation experiment: selecting grapes which are free of mechanical damage and insect disease and are uniform in size and maturity, cutting off the grapes with fruit stalks one by one, washing the grapes with clear water, soaking the grapes into the mixed liquid prepared in the step 4 for 30min, taking out the grapes, naturally drying the grapes, placing the grapes in a storage tray, and taking distilled water as a blank; placing 40 grapes in each tray, and preserving at room temperature; the results are shown in tables 10, 11 and 12;
TABLE 10 influence of the mixture of fruit and vegetable with bactericidal and freshness-keeping effects on the weight loss ratio (%) of grape
TABLE 11 influence of the mixture for sterilizing and refreshing fruits and vegetables on soluble solids (%) of grapes
TABLE 12 influence of the mixture for sterilizing and refreshing fruits and vegetables on the good fruit yield (%) of grapes
The result shows that the treatment of the fruit and vegetable sterilizing and fresh-keeping mixed liquid in the step 4 can prevent microorganisms from entering grape fruits, keep the good fruit rate of grapes, reduce the water dispersion loss and improve the quality index content such as soluble solid matters.
Claims (6)
1. A preparation method of a fruit and vegetable sterilization and preservation complexing agent is characterized by comprising the following steps:
(1) Fatty acid modified Fe 3 O 4 Preparation of nanoenzyme
Dissolving 1.5-3 parts by weight of ammonium ferrous sulfate and 1-2 parts by weight of ferric trichloride in 40-60 parts by weight of deionized water, stirring and heating in a water bath under the protection of nitrogen, adding 4-6 parts by weight of acetonitrile solution containing 0.1-0.5 part by weight of fatty acid when a reaction solution is heated to 80 ℃, stirring the mixed solution for 5-10 min, adding 5-10 parts by weight of ammonia water, continuously stirring the reaction solution at 80 ℃ for 30-60 min, cooling to room temperature, precipitating the obtained suspension with methanol, collecting a product with a magnet, washing with methanol for 4-6 times to remove excessive fatty acid, and performing vacuum drying to obtain the fatty acid modified Fe 3 O 4 Nano-enzyme;
(2) Preparation of loaded nano-enzyme composite liquid
Mixing and heating 30-50 parts by weight of guar gum, 90-100 parts by weight of gellan gum and 2500-3000 parts by weight of distilled water to 80 ℃, stirring and dissolving, and adding 5-10 parts by weight of fatty acid modified Fe after complete dissolution 3 O 4 Continuously stirring the nano enzyme at 80 ℃ for 30-40 min to obtain nano enzyme-loaded composite liquid;
(3) Preparation of composite agent of loaded nano enzyme and glucose oxidase
Heating 20 parts by weight of the nano-enzyme-loaded composite liquid to 80 ℃ for complete dissolution, cooling to 50 ℃, adding 1 part by weight of glucose oxidase, and uniformly stirring to room temperature to obtain a composite agent loaded with the nano-enzyme and the glucose oxidase, namely the fruit and vegetable sterilization and preservation composite agent;
the fatty acid is one of caproic acid, heptanoic acid, caprylic acid and pelargonic acid.
2. The preparation method of the fruit and vegetable sterilization and preservation compound agent according to claim 1, which is characterized in that: the mass volume concentration of the ammonia water is 28%.
3. The preparation method of the fruit and vegetable sterilization and preservation compound agent according to claim 1, which is characterized in that: the gellan gum is low acyl gellan gum or high acyl gellan gum.
4. The preparation method of the fruit and vegetable sterilization and fresh-keeping compound agent according to claim 1, characterized by comprising the following steps: the glucose oxidase activity was 8U/mL.
5. The fruit and vegetable sterilizing and fresh-keeping compound agent prepared by the preparation method of the fruit and vegetable sterilizing and fresh-keeping compound agent according to any one of claims 1 to 4.
6. The fruit and vegetable sterilizing and fresh-keeping complexing agent as defined in claim 5 is applied to fruit and vegetable sterilizing and fresh-keeping, and is characterized in that: 5-10 parts of fruit and vegetable sterilization and preservation complexing agent, 1-2 parts of calcium chloride, 3-8 parts of glycine and 5-10 parts of glucose are mixed, distilled water is added to complement 100 parts by weight, the mixture is stirred and mixed uniformly, fruits to be preserved are immersed in the mixed solution for 10-30 min, and the fruits are taken out, dried, packed in bags and stored at normal temperature or low temperature of 4 ℃.
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| CN109046360A (en) * | 2018-06-11 | 2018-12-21 | 扬州大学 | A kind of Fe that catalytic activity improves3O4Nano enzyme and its preparation method and application |
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| CN108821347A (en) * | 2018-07-08 | 2018-11-16 | 启东祥瑞建设有限公司 | A kind of Fe3O4The preparation method of nano enzyme |
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